Radiation curable coating composition comprising an oligomer and a copolymerizable ultra-violet absorber

ABSTRACT

What is described herein is a radiation curable coating composition comprising: 
     A. An oligomer of Formula I: ##STR1##  wherein: R 1  is hydrogen or methyl; and 
     Y is a divalent urethane residue; and 
     B. a copolymerizable ultra-violet light absorber which is a copolymerizable (2-cyano-3,3-diphenylacryloxy) alkylene ethylenic ether of Formula IV: ##STR2##  where (Ar) 1  and (Ar) 2  are aromatic carbocylic nuclei of the benzene and naphthalene series; 
     X is alkylene, C 2  -C 17 , unsubstituted or substituted; 
     R is alkylene, C 1  -C 10 , oxyalkylene, C 1  -C 10 , alkyleneoxyalkylene, C 1  -C 10  or phenylene, C 1  -C 10 , unsubstituted or substituted with hydroxy, and 
     R&#39; and R&#34; are independently hydrogen or alkyl, C 1  -C 6 . 
     Preferably the coating composition contains a vinyl monomer, such as N-vinyl-2-pyrrolidone or an acrylic acid ester, which is copolymerizable with the oligomer. 
     The process for curing the composition also is disclosed.

BACKGROUND OF THE INVENTION Related Applications

This application is a continuation-in-part of Ser. No. 006,787, filedJan. 26, 1979, now U.S. Pat. No. 4,178,303.

Related subject matter is also found in Ser. No. 022,370, filed Mar. 20,1979, now U.S. Pat. No. 4,202,834.

FIELD OF THE INVENTION

This invention relates to radication curable coating compositionscontaining copolymerizable ultra-violet light absorber compounds, whichcan provide polymer materials with improved degradation to light.

DESCRIPTION OF THE PRIOR ART

Coating compositions which are curable under the influence of radiationin general and ultra-violet light as well as electron beam in particularare well known. Representative examples of prior coating compositionsinclude those disclosed in U.S. Pat. Nos. 3,782,961; 3,829,531;3,850,770; 3,874,906; 3,864,133; 3,891,523; 3,895,171; 3,899,611;3,907,574; 3,912,516; 3,932,356; and 3,989,609. Unfortunately, thesecoating compositions suffer from a number of disadvantages and do nothave an in situ ultraviolet absorber in the composition. Many of thesecoating compositions have insufficient flexibility that causes them tocrack when applied to flexible substrates such as those of polyvinylchloride. Other compositions do not adhere sufficiently to the substratewith the undesirable result that they become dislodged or peel. Stillother coating compositions require the use of solvents that must beevaporated during the curing process. The evaporation of such solventsconsumes energy and creates atmospheric pollution problems. Othercompositions produce coatings that yellow, do not weather well, and haveinsufficient scratch-resistance, stain-resistance, abrasion-resistance,and/or solvent/resistance.

The use of ultra-violet absorbers in plastics or coatings to enhanceweather resistance is known. The absorbers absorb the radiation anddissipate the energy and thus protect the coating from structuraldegradation. Considerable economic saving is realized by incorporatingthe ultra-violet absorber on the surface of a plastic article ratherthan using the ultra-violet absorber in conventional bulk application.Conventional surface application, such as the use of a solvent or paintvehicle is, moreover, undesirable in view of the pollution hazard andbulk handling procedures. Radiation curing has made possible productionof coating films which are easier to handle, but heretofore ultra-violetabsorbers have consumed the energy from the radiation source resultingin too high energy demands in curing or too slow curing rates. If asmall amount of ultraviolet photoinitiator is used to facilitate curing,then addition of use levels of most ultra-violet stabilizers wouldprevent the curing from occurring.

Accordingly, it is an object of the present invention to provide animproved coating composition that is substantially free of one or moreof the disadvantages of prior radiation curable coating compositions.

Yet another object is to provide a coating composition that will producea coating that is weather-resistant, non-yellowing, scratch-resistant,stain-resistant, abrasion-resistant, and solvent-resistant.

Yet another object is to provide a coating composition that is free ofvolatile solvents.

Another object is to provide an improved process for coating substratessuch as those of natural leather, synthetic leather, polyvinyl chloride,polyurethanes and polycarbonates.

Still another object is to provide a coating composition with acopolymerizable ultra-violet absorber which can be cured by radiation.

Other objects and advantages of the present invention will be apparentto those skilled in the art by reference to the following detaileddescription.

SUMMARY OF THE INVENTION

The above and other objects are accomplished according to the presentinvention by providing a coating composition comprising:

A. An oligomer of Formula I: ##STR3## where:

R¹ is hydrogen or methyl;

Y is a divalent urethane residue; and,

B. A copolymerizable (2-Cyano-3,3-diphenylacryloxy) alkylene ethylenicether ultra-violet light absorber having the Formula IV: ##STR4## where:

(Ar)₁ and (Ar)₂ are aromatic carbocyclic nuclei of the benzene andnaphthalene series and are independently selected from phenyl or phenylsubstituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano,acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substitutedphenoxy, or alkoxy phenyl substituted phenyl and naphthyl;

X is alkylene, C₂ -C₁₇, unsubstituted or substituted with halo, cyano,alkyl, C₁ -C₆, alkoxy, C₁ -C₆ alkoxyalkyl, C₁ -C₆ or alkoxyalkyleneoxy,C₁ -C₆ ;

R is alkylene, C₁ -C₁₀, oxyalkylene, C₁ -C₁₀ alkyleneoxyalkylene, C₁-C₁₀ or phenylene, C₁ -C₁₀, unsubstituted or substituted with hydroxy,and,

R' and R" are independently hydrogen or alkyl, C₁ -C₆.

In the best mode of the invention, (Ar)₁ and (Ar)₂ are phenyl, X is --C₂H₄ --, R is alkylene, --CH₂ --, and R' and R" are both hydrogen.

Preferably the composition includes a vinyl monomer or monomers whichare copolymerizable with the oligomers. Suitable vinyl monomers areN-vinyl-2-pyrrolidone and acrylic acid esters.

The oligomers of the present invention are produced by reactingpolytetrahydrofuran or poly caprolactone with a diisocyanate to producean isocyanate terminated prepolymer. The isocyanate terminatedprepolymer is then capped with a capping agent to produce the oligomerof Formula I. The preferred oligomers of Formula I are those of FormulasII and III: ##STR5## wherein:

R¹ is hydrogen or methyl;

R² is lower alkylene;

R³ is aliphatic or cycloaliphatic;

X is --O-- or --NH--; and

n is an integer from 2 to 50 inclusive.

More preferred are the oligomers of formulas (V) and (VI): ##STR6##wherein "n" is an integer from 5 to 20 inclusive.

The polytetrahydrofuran is commercially available from the Du PontCompany under the tradenames "Terrecol-650", "Terrecol-1000", and"Terrecol-2000", and from the Quaker Oats Company under the tradenames"Polymeg-650", "Polymeg-1000", and "Polymeg-2000". In the above namedtradenames the number indicates the approximate molecular weight of thepolytetrahydrofuran. The most preferred polytetrahydrofuran is thathaving a molecular weight of 650 which is consistent with the definitionof "n" in Formulas II and V herein. At higher molecular weights wherein"n" exceeds about 50 the resultant oligomer has too high a viscosity.

The caprolactone polyols are commercially available from Union CarbideCorporation under the tradenames "Niax Caprolactone Polyols"-PCP-0200,PCP-0210, PCP-0230, PCP-0240, PCP-0300, PCP-0301 and PCP-0310. The 0200series are diols with molecular weights 530, 830, 1250 and 2000respectively. The 0300 series are triols with molecular weights 540, 300and 900 respectively.

The oligomers of Formula II, III, V and VI can be produced in accordancewith U.S. Pat. No. 4,129,709. The capping agents useful in the presentinvention are those that will react with the isocyanate terminatedprepolymer to produce the oligomers of Formula II. In general, anycapping agent having a terminal amine or hydroxyl group and also havingan acrylic acid or methacrylic acid moiety is suitable. Examples ofsuitable capping agents include among others hydroxyethyl acrylate,hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate,hydroxypentyl acrylate, hydroxypentyl methacrylate, hydroxyhexylacrylate, hydroxyhexyl methacrylate, aminoethyl acrylate, and aminoethylmethacrylate.

The diisocyanates useful to produce oligomers of Formula II arealiphatic and cycloaliphatic diisocyanates that will react with terminalhydroxyl groups present on the polytetrahydrofuran. Of course, aromaticdiisocyanates undergo the same reaction but do not yield a product assatisfactory as that obtained by the use of aliphatic diisocyanates.Examples of suitable diisocyanates include among others, isophoronediisocyanate, 4,4'-dicyclohexylmethane-diisocyanate availablecommercially from the Du Pont Company under the tradename "Hylene W",and trimethyl-hexamethylene-diisocyanate, 1,6 hexamethylenediisocyanate, 2,4,4 triethyl 1,6 hexylene diisocyanate, octadecylenediisocyanate and 1,4 cyclohexylene diisocyanate. The preferreddiisocyanates are isophorone diisocyanate (3-isocyanatomethyl 3,5,5trimethyl cyclohexyl isocyanate) and 4,4'dicyclohexylmethane-diisocyanate.

The vinyl monomer copolymerizable with the oligomer may be one or moremonomers compatible with the oligomer selected. N-vinyl-2-pyrrolidoneand acrylic acid esters having a boiling point of at least 200° C. at760 mm Hg are preferred. These monomers allow adjustment of theviscosity for ease of coating operations and N-vinyl-2-pyrrolidones alsoenhance the rate of curing.

The weight ratio of oligomer to N-vinyl-2-pyrrolidone can vary widely aslong as the properties of the resultant cured coating composition arenot adversely affected, however, they are generally present in a weightratio of 1:9 to 9:1 and preferably 1:3 and 3:1. At higher ratios, e.g.,those rich in oligomer, the uncured coating composition tends to havetoo high a viscosity. This high viscosity makes it difficult to applythe uncured coating composition to the substrate. At lower ratios theresultant cured coating composition tends to be too hard and inflexible.

The acrylic acid ester should have a boiling point of at least 200° C.at 760 mm Hg. Acrylic acid esters of lower boiling points tend tovaporize during curing. Such vaporization causes undesirable changes inthe coating composition. Furthermore, vaporized acrylic acid esters tendto polymerize on the radiation source, e.g., ultra-violet lamps orelectron beam window. This vaporization also causes undesirableatmospheric pollution. The acrylic acid esters useful in the presentinvention include, among others, monoesters, diesters and higher estersof both acrylic acid and methacrylic acid. Examples of suitable acrylicacid esters include, among others, 1,4-butanedioldiacrylate,1,6-hexanedioldiacrylate, neopentylglycoldiacrylate,pentaerythritol-tetramethacrylate, trimethylolpropanetriacrylate,ethylhexyl-acrylate, ethylhexyl-methacrylate, pentyl-acrylate,hexyl-acrylate and cyclohexyl-methacrylate. 1,4-butanedioldiacrylate and1,6 hexanedioldiacrylate are the preferred acrylic acid esters.

The acrylic acid ester can be present in the coating composition inwidely varying amounts but is generally present in a weight ratio of 1:9to 9:1 and preferably 1:3 to 3:1 compared to the oligomer of Formula Ior II.

The copolymerizable (2-cyano-3,3-diphenylacryloxy) alkylene ethylenicether ultra-violet light absorber is of the Formula IV. ##STR7## where(Ar)₁ and (Ar)₂ are aromatic carbocyclic nuclei of the benzene andnaphthalene series and are independently selected from phenyl or phenylsubstituted with alkyl, halo, alkoxy, carboxy, carbalkoxy, cyano,acetyl, benzoyl, phenyl, alkyl phenyl, phenoxy phenyl, alkyl substitutedphenoxy, or alkoxy phenyl substituted phenyl and naphthyl;

X is alkylene, C₂ -C₁₇, unsubstituted or substituted with halo, cyano,alkyl, alkoxy, C₁ -C₆, alkoxyalkyl, C₁ -C₆ or alkoxyalkyleneoxy, C₁ -C₆; and;

R is alkylene, C₁ -C₁₀, oxyalkylene, C₁ -C₁₀ alkyleneoxyalkylene, C₁-C₁₀ or phenyl, C₁ -C₁₀, unsubstituted or substituted with hydroxy, and,

R' and R" are independently hydrogen or alkyl, C₁ -C₆.

In the best mode of the invention, (Ar)₁ and (Ar)₂ are phenyl, X is --C₂H₄ --, R is alkylene, --CH₂ --, and R' and R" are both hydrogen.

Suitable (Ar)₁ and (Ar)₂ groups are given in U.S. Pat. No. 3,644,466,including representative starting benzophenone compounds. In the bestmode of the invention, both (Ar)₁ and (Ar)₂ are phenyl.

The X groups are unsubstituted or substituted alkylene radicals, C₂-C₁₇. The preferred groups are unsubstituted lower alkylene, C₂ -C₆,which are derived synthetically from ethylene glycol, propylene glycol,butanediol and the like. Typical X groups are --CH₂ CH₂ --; --CH₂ CH₂CH₂ --; --CH₂ CH₂ CH₂ CH₂ --, and the like. The best mode is representedby --CH₂ --CH₂ --.

The --RCR'═CHR" radical is copolymerizable with vinyl monomers so thatthe ultraviolet absorber becomes an integral part of the polymer.Suitable radicals are allyl, crotyl, methylpropenyl, vinylbenzyl,vinyloxyether, allyloxy-2-hydroxypropyl and 2-hydroxy-3-butenyl. Thebest mode is represented by allyl.

The compounds of Formula IV contain both ultra-violet light absorber andcopolymerizable groups in the same molecule. These groups areeffectively separated by the X radical so that each can perform its ownfunction without interference from the other. Thereupon, the absorberportion does not inhibit the copolymerization, and the ethylenic radicaldoes not affect the light absorbing properties of the molecule.

The absorber compounds may be prepared by alkylation of 2-hydroxyalkyl2-cyano-3,3-diphenyl acrylate with an ethylenic halide, as described indetail in the aforementioned copending patent application.

Preferably, in this synthesis, the hydroxy group of a hydroxyalkyl cyanoacetate first is protected by acylation with a group convertible byhydrolysis to the hydroxy compound, e.g. with acetyl chloride, toprovide the corresponding acetoxyalkyl cyanoacetate. The protectedcompound then is condensed with a benzophenone in a Knoevenagel reactionto provide the acetoxyalkyl(2-cyano-3,3-diphenyl) acrylate in goodyield. Subsequent acid hydrolysis of the protecting acetyl group affordsthe corresponding hydroxy intermediate, which is then directly alkylatedwith a suitable ethylenic halide to give the desired compounds.

The amount of ultra-violet absorber of the above formula in the coatingcompositions for radiation curing suitably can vary from 0.5 to 5%;preferably from 0.75 to 2%, and optimally, about 1.5% by weight of thecomposition. Lesser amounts do not give a coating that retains the lighttransmission or low yellowness of the coating. Greater amounts retardthe curing to an unacceptable level.

If the curing is done with ultra-violet light a photo-initiator is used.Suitable photo-initiators include vicinal ketaldonyl compounds (i.e.,compounds containing a ketone group and an aldehyde group) such asdiacetyl, benzil; 2,3-pentanedione, 2,3-octanedione,1-phenyl-1,2-butanedione, 2,2-dimethyl-4-phenyl-3,4-butanedione,phenyl-glyoxal, diphenyl-triketone; aromatic diketones, such asanthraquinone; acryloins, such as benzoin; pivaloin acryloin ethers,such as benzoin-methyl-ether, benzoin-ethyl-ether, benzoin-butyl-ether,benzoin-isobutyl-ether, benzoin-phenyl-ether; alpha-hydrocarbonsubstituted aromatic acyloins, including alpha-methyl-methyl-benzoin,alpha-alkyl-benzoin as in U.S. Pat. No. 2,722,512, and phenylbenzoin;diaryl ketones, such as benzophenone and dinaphthyl ketone; and organicdisulfides, such as diphenyldisulfide. The photoinitiator can alsoinclude a synergistic agent, such as a tertiary amine, to enhance theconversion of photo-absorbed energy to polymerization initiating freeradicals. Diethoxyacetophenone available from Union Carbide Corp.,dimethoxyphenylacetophenone such as Irgacure 651 available fromCiba-Geigy or a benzoin ether such as Vicure 10 available from StaufferChemical Company are preferred. The photo-initiator is present in thecoating composition in an amount sufficient to initiate the desiredpolymerization under the influence of the amount of actinic light energyabsorbed. The coating composition generally contains from 0.01 to 5weight percent of photo-initiator based on the weight of the coatingcomposition.

The coating composition can also contain an addition polymerizationinhibitor to prevent undesirable auto-polymerization of the coatingcomposition in storage prior to use. Examples of suitable additionpolymerization inhibitors include, among others, di(1,4 secbutylamino)benzene available from the DuPont Company under the tradename"Anti-Oxidant 22" and phenothiazine available from Tefenco Chemical Co.The addition polymerization inhibitor is present in an amount sufficientto prevent autopolymerization and is generally present in an amount from100-300 PPM based on the weight of the coating composition.

The coating composition can also contain a surfactant. The preferredsurfactants are silicone surfactants such as that available from the DowCorning Corporation under the tradename "DC-193". The surfactant ispresent in an amount necessary to reduce the surface tension of thecoating composition and reduce its viscosity to the desired level. Thesurfactant generally comprises from 0.1 to 5 weight percent based on theweight of the coating composition.

The coating compositions of the present invention can also contain otherconventional additives, such as flow control and leveling agents,organic and inorganic dyestuffs and pigments, fillers, plasticizers,lubricants and reinforcing agents, such as alumina, silica, clay, talc,powdered glass, carbon black and fiberglass.

The coating compositions of the present invention can be cured byapplying them as a film 0.5 mil thick on the substrate. Curing ispreferably done under an inert atmosphere of nitrogen. The coatingcomposition may be applied as a thin film in any conventional mannersuch as by spraying, brushing, dipping, roll coating and the like.

Conventionally, the film on the substrate is positioned to travel on aconveyor and pass under a source of a free radical generator, such asradiation. The coated side of the substrate is exposed to the radiationfor a time sufficient to effect polymerization and convert the film intoan adherent, tough, flexible coating.

As used herein the term radiation refers to any radiation source whichwill produce free radicals and induce addition polymerization of vinylbonds. The actinic radiation is suitably in the wave length of 2000-7500A, preferably 2000 to 4000. A class of actinic light useful herein isultra-violet light and other forms of actinic radiation are from thesun, artificial sources such as Type RS sunlamps, carbon arc lamps.Xenon arc lamps. mercury vapor lamps, tungsten halide lamps, lasers,fluorescent lamps with ultra-violet light emitting phosphors.

Ultra-violet curing rates greater than 20 ft/min/lamp must be obtainedin order to be commercially acceptable. With a reasonable thickness(less than 10 mils) coating compositions with the ultra-violet absorberof Formula IV, present in an amount from 0.5 to 3% based on the weightof the composition, can be cured at rates of 25-50 ft/min/lamp.

The preferred electron beam system contains a wide curtain of electronsdirectly from a linear cathode. A curtain of electrons from the gun'scathode, accelerated to a high velocity by a 200 KV potential, emergesfrom the chamber through a foil window into the coated substrates(Electroncurtain™ by Energy Sciences, Inc.).

The electron beam curing of the coating compositions as described aboveis cured at less than 5 Mrads and generally at 2 Mrads. Curing atgreater than 8 Mrads is deemed unacceptable because of the high cost.

Laminates of film coatings based on acryl urethanes with an ultra-violetabsorber of (2-cyano-3,3-diphenylacryloyloxy) alkylene ethylenic etherapplied on clear polyvinylchloride are surprisingly non-leachable and donot yellow.

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise indicated.These non-limiting examples are illustrative of certain embodimentsdesigned to teach those skilled in the art how to practice the inventionand to represent the best mode contemplated for carrying the invention.

EXAMPLE 1 Preparation of Radiation Cured Coating

Into a dry 1 l. resin kettle fitted with an air inlet tube, a stirrer,thermometer, and dropping funnel was charged 300.8 g. (1.3 moles) ofisophorone diisocyanate and 4.8 ml. of a 10% (W/V) solution ofdibutyltin dilaurate catalyst in ethylhexylacrylate. Dry air then wasbubbled through the stirred solution while 322.1 g. (0.61 moles) ofpolyolcaprolactone (PCP-200) was added dropwise over 45 minutes. Thesolution then was heated to 80° C. and the reactants maintained at thistemperature for 30 minutes. After cooling to 55° C., 160 mg. ofphenothiazine was admixed. Then 151.9 g. (1.3 moles) of hydroxyethylacrylate was added rapidly. The temperature was raised to 80° C. andmaintained for 2 hours.

The resulting oligomer (58.1 g.) was formulated for coating by mixingwith 25.4 g. of ethylhexylacrylate, 16.8 g. of vinyl pyrrolidone, 14.2g. of hexanediol diacrylate, 1.8 g. of DC-193 silicone surfactant, 2.4g. of Vicure-10 photoinitiator and 2.5 g. of2-(2-cyano-3,3-diphenylacryloxy) ethyl allyl ether. The resulting syrupwas coated onto a polyvinyl chloride plate to form a film having athickness of 1.5 mil. The film then was cured by ultraviolet radiationunder an inert atmosphere to provide a tough, clear coating containingthe copolymerized UV absorber compound of the invention. The protectedpolyvinyl chloride film showed less tendency to yellowing in aWeather-Ometer test than on unprotected film.

While certain preferred embodiments of the present invention have beenillustrated by way of specific example it is to be understood that thepresent invention is in no way to be deemed as limited thereto butshould be construed as broadly as all or any equivalents thereof.

What is claimed is:
 1. A radiation curable coating compositioncomprising:A. An oligomer of Formula I: ##STR8## wherein: R¹ is hydrogenor methyl; and Y is a divalent urethane residue; and B. acopolymerizable ultra-violet light absorber compound of Formula IV:##STR9## where: (Ar)₁ and (Ar)₂ are aromatic carbocyclic nuclei of thebenzene and naphthalene series and are independently selected fromphenyl or phenyl substituted with alkyl, halo, alkoxy, carboxy,carbalkoxy, cyano, acetyl, benzoyl, phenyl, alkyl phenyl, phenoxyphenyl, alkyl substituted phenoxy, or alkoxy phenyl substituted phenyland naphthyl; X is alkylene, C₂ -C₁₇, unsubstituted or substituted withhalo, cyano, alkyl, C₁ -C₆, alkoxy, C₁ -C₆ alkoxyalkyl, C₁ -C₆, oralkoxyalkyleneoxy, C₁ -C₆ ; R is alkylene, C₁ -C₁₀, oxyalkylene, C₁ -C₁₀alkyleneoxyalkylene, C₁ -C₁₀ phenylene, C₁ -C₁₀, unsubstituted orsubstituted with hydroxy; and R' and R" are independently hydrogen oralkyl, C₁ -C₆.
 2. The coating composition of claim 1 further comprisinga vinyl monomer copolymerizable with the oligomer.
 3. The coatingcomposition of claim 1 further comprising an addition polymerizationinhibitor present in an amount sufficient to avoid theauto-polymerization of the composition during storage.
 4. The coatingcomposition of claim 3 wherein the addition polymerization inhibitor ispresent in an amount from 100-300 PPM weight percent based upon theweight of the composition.
 5. The coating composition of claim 3 whereinthe weight ratio of oligomer to vinyl monomer is from 1:9 to 9:1.
 6. Thecoating composition of claim 1 further comprising a photo-inhibitorpresent in an amount sufficient to initiate the desired polymerizationunder the influence of the amount of actinic light energy absorbed. 7.The coating composition of claim 1 wherein the ultra-violet lightabsorber is present in an amount from 0.5 to 5 weight percent based onthe weight of the composition.
 8. A composition according to claim 1 inwhich in Formula IV both (Ar)₁ and (Ar)₂ are phenyl.
 9. A compositionaccording to claim 1 in which in Formula IV, X is alkylene, C₂ -C₆. 10.A composition according to claim 1 in which in Formula IV, RCR'═CHR" isallyl, crotyl, methylpropenyl, vinylbenzyl, vinyloxyether,allyloxy-2-hydroxypropyl or 2-hydroxy-3-butenyl.
 11. A compositionaccording to claim 1 in which in formula, IV (Ar)₁ and (Ar)₂ are phenyl,X is alkylene, C₂ -C₆, and --RCR'═CHR" is allyl.
 12. A compositionaccording to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloxy) ethyl allyl ether.
 13. A compositionaccording to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloxy) ethyl 2-methyl-2-propenyl ether.
 14. Acomposition according to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloxy) ethyl 2-methyl-2-propenyl ether.
 15. Acomposition according to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloxy) ethyl vinylbenzyl ether.
 16. Acomposition according to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloyloxy) ethyl 3-allyloxy-2-hydroxypropylether.
 17. A composition according to claim 1 in which Formula IV is2-(2-cyano-3,3-diphenylacryloyloxy) ethyl 2-hydroxy-3-butenyl ether. 18.A coating composition of claim 1 which is photopolymerizable in thepresence of ultra-violet light to produce an adherent coating that isweather-resistant, flexible, scratch-resistant, stain-resistant,abrasion-resistant, and solvent-resistant, said coating compositionconsisting essentially of:A. an oligomer of Formula II: ##STR10##wherein: R¹ is hydrogen or methyl;R² is lower alkylene; R³ is aliphaticor cycloaliphatic; X is --O-- or --NH--; n is an integer from 2 to 50inclusive; B. N-vinyl-2-pyrrolidone; C. hexanediol diacrylate; D.2-(2-cyano-3,3-diphenylacryloxy) ethyl allyl ether present in an amountfrom 0.5 to 5 weight percent based on the weight of the composition; E.a photo-initiator present in an amount from 0.01 to 5 weight percentbased on the weight of the composition; F. an addition polymerizationinhibitor present in an amount from 100-300 PPM based on the weight ofthe composition; G. a silicone surfactant present in an amount from 0.1to 5 percent based on the weight of the composition, wherein the ratioA:B is from 1:3 to 3:1; and wherein the ratio A:C is from 1:3 to 3:1.19. A coating composition of claim 1 which is photopolymerizable in thepresence of ultra-violet light to produce an adherent coating that isweather-resistant, flexible, scratch-resistant, stain-resistant,abrasion-resistant and solvent-resistant, said coating compositionconsisting essentially of:A. an oligomer of Formula III: ##STR11##wherein: R¹ is hydrogen or methyl;R² is lower alkylene; R³ is aliphaticor cycloaliphatic; X is --O-- or --NH--; n is an integer from 2 to 50inclusive; B. N-vinyl-2-pyrrolidone; C. hexanediol diacrylate D.2-(2-cyano-3,3-diphenylacryloxy) ethyl allyl ether present in an amountfrom 0.5 to 3 weight percent based on the weight of the composition; E.a photo-initiator present in an amount from 0.01 to 5 weight percentbased on the weight of the composition; F. an addition polymerizationinhibitor present in an amount from 100-300 PPM based on the weight ofthe composition; G. a silicone surfactant present in an amount from 0.1to 5 percent based on the weight of the composition, wherein the ratioA:B is from 1:3 to 3:1; and wherein the ratio A:C is from 1:3 to 3:1.20. A process for coating a substrate comprising in sequence the stepsof:I. contacting the substrate with a coating composition according toclaim 6, wherein the amount of B. is 0.5 to 5 weight percent based onthe weight of the composition; and, II. exposing the coated substrate toactinic radiation until an adherent dry polymerized weather-resistantcoating is formed on the substrate.
 21. A laminate comprising a planarsheet of clear polyvinyl chloride with a film coating 0.1 to 10 mils inthickness comprising a cured coating composition of claim 1.